Nanoscale Mass Spectrometry Multimodal Imaging via Tip-Enhanced Photothermal Desorption.

Materials ranging from adhesives, pharmaceuticals, lubricants, and personal care products are traditionally studied using macroscopic characterization techniques. However, their functionality is in reality defined by details of chemical organization on often noncrystalline matter with characteristic length scales on the order of microns to nanometers. Additionally, these materials are traditionally difficult to analyze using standard vacuum-based approaches that provide nanoscale chemical characterization due to their volatile and beam-sensitive nature. Therefore, approaches that operate under ambient conditions need to be developed that allow probing of nanoscale chemical phenomena and correlated functionality. Here, we demonstrate a tool for probing and visualizing local chemical environments and correlating them to material structure and functionality using advanced multimodal chemical imaging on a combined atomic force microscopy (AFM) and mass spectrometry (MS) system using tip-enhanced photothermal desorption with atmospheric pressure chemical ionization (APCI). We demonstrate enhanced performance metrics of the technique for correlated imaging and point sampling and illustrate the applicability for the analysis of trace chemicals on a human hair, additives in adhesives on paper, and pharmaceuticals samples notoriously difficult to analyze in a vacuum environment. Overall, this approach of correlating local chemical environments to structure and functionality is key to advancing research in many fields ranging from biology, to medicine, to material science.

Probing static discharge of polymer surfaces with nanoscale resolution.

Triboelectric charging strongly affects the operation cycle and handling of materials and can be used to harvest mechanical energy through triboelectric nanogenerator set-up. Despite ubiquity of triboelectric effects, a lot of mechanisms surrounding the relevant phenomena remain to be understood. Continued progress will rely on the development of rapid and reliable methods to probe accumulation and dynamics of static charges. Here, we demonstrate in-situ quantification of tribological charging with nanoscale resolution, that is applicable to a wide range of dielectric systems. We apply this method to differentiate between strongly and weakly charging compositions of industrial grade polymers. The method highlights the complex phenomena of electrostatic discharge upon contact formation to pre-charged surfaces, and directly reveals the mobility of surface charges. Systematic characterization of commercial polyethylene terephthalate samples revealed the compositions with the best antistatic properties and provided an estimate of characteristic charge density up to 5×10^-5 C/m². Large-scale molecular dynamics simulations were used to resolve atomistic level structural and dynamical details revealing enrichment of oxygen containing groups near the air-interface where electrostatic charges are likely to accumulate.

Multimodal Evidence of Mesostructured Calcium Fatty Acid Deposits in Human Hair and Their Role on Hair Properties.

We provide the first conclusive evidence for the presence of exogenous calcium fatty acid deposits, which not only form in-between the cuticle layers in the lipid-rich cell membrane complex, but also grow to dimensions large enough to cause the structure to bulge, thereby impacting the optical and mechanical properties of the hair fiber. The composition and phase of these deposits were probed using a multimodal analytical approach with spatially resolved techniques including synchrotron micro X-ray fluorescence coupled with X-ray scattering, focused ion beam (FIB)-scanning electron microscopy (SEM), scanning transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared and Raman imaging where the collective analysis is consistent with a meso-phase composed of calcium C16/C18 saturated fatty acids from natural sources such as sebum. X-ray microtomography and serial "slice and view" FIB/SEM both reveal the location and volumetric shape of the deposits.

Mesoporous bragg stack color tunable sensors.

Herein we report a novel self-assembly synthesis, structural and optical characterization of mesoporous Bragg stacks (MBS) composed of spin-coated multilayer stacks of mesoporous TiO(2) and mesoporous SiO(2). Investigation of the optical response of MBS to the infiltration of alcohols and alkanes into its pores reveals better sensitivity and selectivity than conventional Bragg reflectors. Furthermore, we demonstrate that the chemical sensing ability can be tuned via layer thickness, composition and surface properties.

Evolution of nanocrystallinity in periodic mesoporous anatase thin films.

Herein we report the first kinetic study of the intrachannel wall phase-transition of amorphous titania to nanocrystalline anatase for periodic mesoporous titania thin films, monitored by time-resolved in situ high-temperature X-ray diffraction. Structural transformations associated with the phase transition are further probed by high-resolution scanning electron microscopy and transmission electron microscopy. The model found to be most consistent with the kinetic data involves 1D diffusion-controlled growth of nanocrystalline anatase within the spatial confines of the channel walls of the mesostructure. The observation of anisotropic, rod-shaped anatase nanocrystals preferentially aligned along the channel axis implies that the framework of the liquid-crystal-templated mesostructure guides the crystal growth.

Towards flexible inorganic "mesomaterials": one-pot low temperature synthesis of mesostructured nanocrystalline titania.

We hereby report a simple route for the low temperature synthesis of mesoporous nanocrystalline titania involving brief hydrothermal treatment of butanolic precursors and non-ionic tri-block-copolymer surfactant at 100 degrees C, followed by evaporation induced self assembly to make a crack-free flexible film. At no time in the film-forming process is a temperature of more than 120 degrees C reached, thereby permitting the use of substrates that are not stable to higher temperatures.

Lanthanum strontium manganite/yttria-stabilized zirconia nanocomposites derived from a surfactant assisted, co-assembled mesoporous phase.

A one-pot, soft-chemistry, surfactant-assisted co-assembly approach to prepare La(1-x)Sr(x)MnO(3) (LSM)/Y(2)O(3)-stabilized ZrO(2) (YSZ) nanocomposites for use as solid oxide fuel cell (SOFC) cathodes has been investigated. This material with sub-hundred nanometer grain sizes for each phase is the first such nanocomposite where aqueous-based precursors of each component are incorporated in a single synthetic step. This approach utilizes the co-assembly of an anionic yttrium/zirconium acetatoglycolate gel, cetyltrimethylammonium bromide as the cationic surfactant template, and inorganic La, Mn, and Sr salts under alkaline aqueous conditions. The resulting as-synthesized product is an amorphous mesostructured organic/inorganic composite, which is transformed to a mesoporous inorganic oxide with nanocrystalline YSZ walls upon calcination. Calcination to temperatures above 600 degrees C lead to collapse of the mesopores followed by further crystallization of the nanocrystalline YSZ phase and a final crystallization of the LSM perovskite phase above 1000 degrees C. Both the fully crystalline LSM/YSZ and the mesoporous intermediate phase have been investigated for phase homogeneity by TEM energy-dispersive X-ray spectroscopy (EDX) mapping and spot analysis which confirm the dispersion of LSM within a YSZ matrix at the nanometer scale. Impedance spectroscopy analysis of LSM/YSZ nanocomposite electrodes demonstrate a low polarization resistance of around 0.2 omega cm(2) with an activation energy (E(a)) as low as 1.42 eV. Cathodic polarization studies show stable current densities over a 40 h test demonstration.

Practical solid oxide fuel cells with anodes derived from self-assembled mesoporous-NiO-YSZ.

Solid oxide fuel cells comprised of an anode made from sintered and reduced mesoporous-NiO-YSZ are shown to provide stable current and power densities at the operating temperature of 800 degrees C and show better performance than cells with anode cermets made from mechanical mixtures of NiO and YSZ, attributable to the unique anode microstructure.